ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The formation of a chromic ester as an intermediate in the chromic acid oxidation of secondary (and by analogy of primary) alcohols is strongly suggested by a study of the kinetics and deuterium isotope effect in the oxidation of an alcohol with a strongly sterically hindered hydroxyl group. For this alcohol (3β,28-diacetoxy-6β-hydroxy-18β-12-oleanene), either the formation of the ester or (in part) its decomposition can be made rate-limiting. When the reaction is carried out in the presence of mineral acid in solvents of high acetic acid content, the esterification is presumably rate-limiting, since kH/kD is 1.0; when the reaction occurs in 60% aqueous acetic acid in the presence of sodium acetate, both esterification and the decomposition of the ester contribute to the kinetics, since the isotope effect reaches a value of about 2.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19620450725
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